CN103160087A - Completely-biodegradable plasticizing polylactic resin and method for preparing same - Google Patents
Completely-biodegradable plasticizing polylactic resin and method for preparing same Download PDFInfo
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- CN103160087A CN103160087A CN2013101018440A CN201310101844A CN103160087A CN 103160087 A CN103160087 A CN 103160087A CN 2013101018440 A CN2013101018440 A CN 2013101018440A CN 201310101844 A CN201310101844 A CN 201310101844A CN 103160087 A CN103160087 A CN 103160087A
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Abstract
The invention provides a completely-biodegradable plasticizing polylactic resin and a method for preparing the polylactic resin and belongs to the field of modification of polymer materials. The polylactic resin is prepared from polylactic acid, a plasticizing modifying agent, a nucleating agent and an oxidation resisting agent at the mass ratio of 100:(10-40):(0.3-1):(0.3-1). The melt flow rate of the polylactic resin provided by the invention can be controlled at 5-30g/10min, the tensile elongation at break is 480%, the impact strength is 30.0KJ/m<2>, the purposes of plasticizing and toughening the polylactic acid are achieved, the resin has good transparency and complete biodegradability and the application space of the polylactic acid is extended.
Description
Technical field
The present invention relates to the polymer modification field, particularly a kind of complete biodegradable plasticized poly lactic acid resin and preparation method thereof.
Background technology
Poly(lactic acid) be the lactic acid that obtained by the vegetalitas polysaccharide fermentation through the compound that polymerization forms, be a kind of novel recyclable organism degradable material.Poly-lactic acid products can biological degradation, realizes the circulation at occurring in nature, is therefore desirable Green Polymer Material.Poly(lactic acid) also has the good transparency and processibility, thereby poly-lactic acid material has a wide range of applications at wrapping material, fiber and non-woven fabric and medicine and hygiene fields.
Outside the product decapacitation biological degradation of being made by poly(lactic acid), biocompatibility, glossiness, the transparency, feel and good heat resistance, also have certain fungus resistance, flame retardant resistance and ultraviolet-resistent property, therefore purposes is very extensive, can be used as wrapping material, fiber and non-woven fabric etc., be mainly used at present the fields such as clothes (underwear, coat), industry (building, agricultural, forestry, papermaking) and health care.Poly(lactic acid) is applicable to the various working methods such as blowing, injection moulding, and is easy to process, uses very extensive.Can be used for processing from industry to civilian various plastics, wrap food, fast food lunch-box, non-woven fabrics, industry and civilian cloth.And then being processed into geotextile, health care fabric, rag, sanitary product, outdoor Uvr Protective Fabric, tent cloth, ground cushion face etc., market outlook are very good.Poly(lactic acid) consistency and degradability are good, and be also very extensive in the field of medicaments application, and as producing the disposable infusion apparatus, exempting to tear open type operating sutures etc., low molecular weight pdlla is done medicament slow release packing agent etc.But poly(lactic acid) fragility is larger, poor toughness, and resistance to impact shock is less than 5KJ/m
2, seriously restricted the range of application of poly(lactic acid).
in order to improve the toughness of poly(lactic acid), mostly prior art is to adopt the method for polycomponent blending and modifying toughness reinforcing, for example: select the small molecules softening agent to carry out toughening modifying to poly(lactic acid), object lesson as use the citric acid compounds prepare citric acid plasticization and modification poly(lactic acid) (citric acid plasticization and modification poly(lactic acid). polymer material science and engineering, (2008), 24 (1), 151-154), perhaps use epoxy soybean oil to prepare plasticization and modification poly(lactic acid) (Thermal, mechanicalandrheologicalpropertiesofpoly (lacticacid)/epoxidizedsoybeanoilblends.PolymerBulletin, (2009), 62 (1), 91-98), though adopt aforesaid method can improve toughness of material to after polylactic acid modified, but small molecules easily moves, therefore As time goes on the performance of this kind material can occur deteriorated, affect the work-ing life of material, and the poly(lactic acid) after modification generally is difficult to keep original transparency.in order to address the above problem, application number is that 200510067228 Chinese patent literature discloses the method for the transparent material that a kind of production made by poly(lactic acid) and the transparent material of being made by poly(lactic acid), the method is that the monomer that has two or more pairs of keys in poly(lactic acid) and its molecule is mediated jointly, and at high temperature molding is mediated product acquisition moulded parts, moulded parts quenches after molding, in quenching process, moulded parts carries out crosslinking Treatment, prevent that polylactic acid molecule from carrying out recrystallize, make thus transparent polylactic acid article, but the biodegradability that adopts this method to carry out the cross-linking polylactic acid that obtains after crosslinking Treatment reduces greatly.
Summary of the invention
The objective of the invention is to satisfy simultaneously the problem of high tenacity, completely biodegradable and high-clarity in order to solve existing polylactic resin, and a kind of complete biodegradable plasticized poly lactic acid resin and preparation method thereof is provided.
At first the present invention provides a kind of complete biodegradable plasticized poly lactic acid resin, comprise: poly(lactic acid), poly-diethylene glycol adipate, nucleator and oxidation inhibitor, the weight ratio of described poly(lactic acid), poly-diethylene glycol adipate, nucleator and oxidation inhibitor is 100:(10～40): (0.3～1): (0.3～1).
Preferably, the number-average molecular weight of described poly(lactic acid) is 50000～200000 dalton.
Preferably, the number-average molecular weight of described poly-diethylene glycol adipate is 1000～20000 dalton.
Preferably, described nucleator is multiamide compounds or calcium carbonate load phenyl-phosphonic acid calcium.
Preferably, described multiamide class mixture is TMC-300 or TMC-328.
Preferably, described oxidation inhibitor is the mixture of four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.
Preferably, the weight ratio of described four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is 1:(1.5～2.5).
The present invention also provides a kind of preparation method of complete biodegradable plasticized poly lactic acid resin, comprises as follows:
After being mixed, poly(lactic acid), nucleator and oxidation inhibitor adds poly-diethylene glycol adipate, obtain mixture, with said mixture at 130 ℃～195 ℃ blending extrusions, obtain polylactic resin, the blending ratio of described poly(lactic acid), poly-diethylene glycol adipate, nucleator and oxidation inhibitor is counted by weight: 100:(10～40): (0.3～1): (0.3～1).
Preferably, the number-average molecular weight of described poly-diethylene glycol adipate is 1000～20000 dalton.
Preferably, described nucleator is multiamide compounds or calcium carbonate load phenyl-phosphonic acid calcium.
Beneficial effect of the present invention
A kind of complete biodegradable plasticized poly lactic acid resin provided by the invention, comprise poly(lactic acid), poly-diethylene glycol adipate, nucleator and oxidation inhibitor, the weight ratio of described poly(lactic acid), poly-diethylene glycol adipate, nucleator and oxidation inhibitor is 100:(10～40): (0.3～1): (0.3～1), wherein on poly-diethylene glycol adipate molecular chain, ehter bond is arranged, Chain Flexibility is good, it is used for improving the snappiness of poly(lactic acid) for properties-correcting agent, gives the higher shock resistance of material after blend; Poly-diethylene glycol adipate molecular weight is high, and is not volatile and separate out than the anti-migration of small molecules softening agent, can prevent the performance degradation that polylactic acid article causes because of plasticizer migration; In addition, the refractive index that poly-diethylene glycol adipate and poly(lactic acid) are all transparent material and itself and poly(lactic acid) is close, thereby will still can keep higher transparency after itself and polylactic acid blend; And poly-diethylene glycol adipate is a kind of compound of fully biodegradable, therefore with the fully biodegradable still of the material after itself and polylactic acid blend.Therefore, use poly-diethylene glycol adipate can not affect the original transparency of material and completely biodegradable when improving poly(lactic acid) toughness as the properties-correcting agent of poly(lactic acid); Can promote poly(lactic acid) to improve poly(lactic acid) crystallization velocity and degree of crystallinity after nucleator adds in the course of processing, improve forming process and thermotolerance; The free radical depolymerization occurs when ultraviolet long-term irradiation or the high temperature in adding be used to suppressing above-mentioned polymkeric substance of oxidation inhibitor, improves thermotolerance and the weathering resistance of material.With respect to existing polylactic resin, polylactic resin resistance to impact shock provided by the invention reaches 30.0KJ/m
2Tension fracture elongation rate reaches 480%, reached polylactic acid plasticize and toughness reinforcing purpose, a kind of complete biodegradable plasticized poly lactic acid resin provided by the invention has high-clarity and completely biodegradable simultaneously, and then has expanded the application space of poly-lactic acid material.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just as further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
At first the present invention provides a kind of complete biodegradable plasticized poly lactic acid resin, comprise: poly(lactic acid), poly-diethylene glycol adipate, nucleator and oxidation inhibitor, in parts by weight, the weight ratio of described poly(lactic acid), poly-diethylene glycol adipate, nucleator and oxidation inhibitor is 100:(10～40): (0.3～1): (0.3～1).
In above-mentioned polylactic resin, poly(lactic acid) is as basic components, give the higher tensile strength of material and ductility, preferred number average molecular weight is 50000～200000 daltonian poly(lactic acid), the poly(lactic acid) mechanical property that molecular weight is lower is relatively poor, too high its viscosity that makes of polylactic acid molecule amount is too high, adds be difficult to man-hour and gather the diethylene glycol adipate blend.
Poly-diethylene glycol adipate in above-mentioned polylactic resin is plasticization modifier, toughness with raising material after polylactic acid blend, on poly-diethylene glycol adipate molecular chain, ehter bond is arranged, Chain Flexibility is good, it is used for improving the snappiness of poly(lactic acid) for properties-correcting agent, gives the higher shock resistance of material after blend; Poly-diethylene glycol adipate molecular weight is high, and is not volatile and separate out than the anti-migration of small molecules softening agent, can prevent the performance degradation that polylactic acid article causes because of plasticizer migration; In addition, the refractive index that poly-diethylene glycol adipate and poly(lactic acid) are all transparent material and itself and poly(lactic acid) is close, thereby will still can keep higher transparency after itself and polylactic acid blend; And poly-diethylene glycol adipate is a kind of compound of fully biodegradable, therefore with the fully biodegradable still of the material after itself and polylactic acid blend.Therefore, use poly-diethylene glycol adipate can not affect the original transparency of material and completely biodegradable when improving poly(lactic acid) toughness as the properties-correcting agent of poly(lactic acid).
The weight ratio of poly-diethylene glycol adipate of the present invention and poly(lactic acid) is (10～40): 100, be preferably (20～30): 100, the raising of poly-diethylene glycol adipate content is conducive to improve the shock resistance of polylactic resin, but too high levels makes the strength of materials after blend significantly descend.Preferably selecting number-average molecular weight is 1000～20000 daltonian poly-diethylene glycol adipates.The viscosity of the poly-diethylene glycol adipate that molecular weight is too high is excessive, adds that be difficult to man-hour and polylactic acid blend, and the too high elongation at break that also can reduce composition of molecular weight; The too low similar small molecules softening agent of molecular weight of poly-diethylene glycol adipate easily migrates to material surface, affects the work-ing life of material.
Of the present invention add nucleator in the mixed system of poly(lactic acid) and poly-diethylene glycol adipate after, nucleator can be as the out-phase crystallization nucleus of poly(lactic acid), improve poly(lactic acid) crystallization velocity and degree of crystallinity in the course of processing, improve forming process and thermotolerance, in polylactic resin, the weight ratio of poly(lactic acid) and nucleator is 100:(0.3～1).Nucleator of the present invention is preferably multiamide compounds or calcium carbonate load phosphenylic acid calcium.Described multiamide class mixture is preferably the nucleator that model is TMC-300 or TMC-328; To be phosphenylic acid calcium that phenyl-phosphonic acid and calcium carbonate reaction are generated load on the calcium carbonate surface as activeconstituents described calcium carbonate load phosphenylic acid calcium obtains, concrete grammar is: calcium carbonate is disperseed in acetone or chloroform, add again phenyl-phosphonic acid, at room temperature stir 4h, then centrifugation, filtration obtains white precipitate, throw out is washed with acetone or chloroform, the unreacted phenyl-phosphonic acid of Ex-all, dry sediment, obtaining calcium carbonate load phenyl-phosphonic acid calcium, is the Chinese patent of CN102212257A referring to publication number.The weight ratio of described calcium phosphate and phenyl-phosphonic acid is (5～40): 1, and described calcium carbonate is preferably nanometer grade calcium carbonate.
Of the present invention add oxidation inhibitor in the mixed system of poly(lactic acid) and poly-diethylene glycol adipate after, oxidation inhibitor can react because of free radical light-initiated or that thermal initiation generates with poly(lactic acid) and poly-diethylene glycol adipate, and then prevent that above-mentioned polymkeric substance from the free radical depolymerization occuring when ultraviolet long-term irradiation or high temperature, eliminate ultraviolet ray to the Oxidative demage of polylactic resin goods, improve thermotolerance and the weathering resistance of material, in polylactic resin, the weight ratio of poly(lactic acid) and oxidation inhibitor is 100:(0.3～1).
The oxidation inhibitor that the present invention uses is preferably selected four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) mixture of ester, above-mentioned two kinds of compounds and with after can obviously promote antioxidant effect, and the processing temperature of suitable this co-mixing system.In oxidation inhibitor, the weight ratio of four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is preferably 1:(1.5～2.5), 1:2 more preferably.
The present invention also provides the preparation method of above-mentioned polylactic resin, comprising:
Add 10～40 parts of poly-diethylene glycol adipates after the nucleator of 100 parts of poly(lactic acid) and 0.3～1 part, the oxidation inhibitor of 0.3～1 part are mixed, will add mixture after poly-diethylene glycol adipate at 130 ℃～195 ℃ blending extrusions, obtain polylactic resin.
hybrid mode for poly(lactic acid) and nucleator, oxidation inhibitor can be method well known to those skilled in the art, and as in stirrer for mixing, there is no particular restriction to this in the present invention, can be method well known to those skilled in the art for the method with the blending extrusion of poly(lactic acid) and poly-diethylene glycol adipate, preferred blending extrusion in twin screw extruder, forcing machine one district's temperature more preferably is set is: 130 ℃～150 ℃, two district's temperature are 140 ℃～180 ℃, three district's temperature are 145 ℃～190 ℃, four district's temperature are 150 ℃～195 ℃, five district's temperature are 160 ℃～195 ℃, six district's temperature are 160 ℃～190 ℃, seven district's temperature are 150 ℃～190 ℃, head temperature is 145 ℃～175 ℃, screw speed preferably is made as 100rpm～300rpm, obtain polylactic resin after extruding pelletization.
In order further to understand the present invention, below in conjunction with embodiment, poly-diethylene glycol adipate provided by the invention and preparation method thereof is described.Poly(lactic acid) in following examples provides by Zhejiang Hisun Biomaterials Co., Ltd, and model is EVODE201; Poly-diethylene glycol adipate is provided by Changchun Zhongke Yinghua Special Materials Co., Ltd; Nucleator is provided by Shanxi Province chemical research institute, is the multiamide compounds, and model is TMC-300 or TMC-328; Antioxidant 1010 is provided by Beijing Jiyi Chemicals Co., Ltd., and model is JY-1010, and irgasfos 168 is provided by Beijing Jiyi Chemicals Co., Ltd., and model is JY-168; In following examples, tensile property is that the standard of GB/T1010.3-2006 is tested; Resistance to impact shock is to test according to the standard of ASTMD-256; Transmittance and mist degree are the tests that the material take thickness as 0.04mm carries out.
Embodiment 1
1, take by weight following component:
2, after being mixed, above-mentioned poly(lactic acid) and antioxidant 1010 and irgasfos 168 added stirrer for mixing 5 minutes, mixed raw material is added in twin screw extruder, in extrusion, the forcing machine side line quantitatively adds above-mentioned poly-diethylene glycol adipate with peristaltic pump, the forcing machine parameter is set lists in table 1, obtain polylactic resin after extruding pelletization, mechanical property and the transmittance of test polylactic resin, test result is listed in table 2.
Embodiment 2
1, take by weight following component:
2, this step operation is identical with embodiment 1, and the forcing machine processing parameter is listed in table 1, obtains polylactic resin after extruding pelletization, mechanical property and the transmittance of test polylactic resin, and test result is listed in table 2.
Embodiment 3
1, take by weight following component:
2, this step operation is identical with embodiment 1, and the forcing machine processing parameter is listed in table 1, obtains polylactic resin after extruding pelletization, mechanical property and the transmittance of test polylactic resin, and test result is listed in table 2.
Embodiment 4
1, take by weight following component:
2, this step operation is identical with embodiment 1, and the forcing machine processing parameter is listed in table 1, obtains polylactic resin after extruding pelletization, mechanical property and the transmittance of test polylactic resin, and test result is listed in table 2.
Embodiment 5
1, take by weight following component:
2, this step operation is identical with embodiment 1, and the forcing machine processing parameter is listed in table 1, obtains polylactic resin after extruding pelletization, mechanical property and the transmittance of test polylactic resin, and test result is listed in table 2.
Embodiment 6
1, take by weight following component:
2, this step operation is identical with embodiment 1, and the forcing machine processing parameter is listed in table 1, obtains polylactic resin after extruding pelletization, mechanical property and the transmittance of test polylactic resin, and test result is listed in table 2.
Embodiment 7
1, take by weight following component:
2, this step operation is identical with embodiment 1, and the forcing machine processing parameter is listed in table 1, obtains polylactic resin after extruding pelletization, mechanical property and the transmittance of test polylactic resin, and test result is listed in table 2.
Embodiment 8
1, take by weight following component:
2, this step operation is identical with embodiment 1, and the forcing machine processing parameter is listed in table 1, obtains polylactic resin after extruding pelletization, mechanical property and the transmittance of test polylactic resin, and test result is listed in table 2.
Forcing machine processing parameter in table 1 embodiment 1～8
Table 2 polylactic resin mechanical property and transmittance test result
By the above results as can be known, polylactic resin plasticization effect provided by the invention is better, and tension fracture elongation rate is up to 480%, and resistance to impact shock reaches 30.0KJ/m
2Tensile strength can reach 26.4MPa, material has higher transparency simultaneously, because the poly(lactic acid) in blend and poly-diethylene glycol adipate all have completely biodegradable, therefore polylactic resin provided by the invention has guaranteed the completely biodegradable of composition when improving toughness, keeping transparency, makes poly-lactic acid material have more wide application space.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be apparent concerning those skilled in the art, and General Principle as defined herein can be in the situation that do not break away from the spirit or scope of the present invention, realization in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. complete biodegradable plasticized poly lactic acid resin, it is characterized in that, comprise: poly(lactic acid), poly-diethylene glycol adipate, nucleator and oxidation inhibitor, the weight ratio of described poly(lactic acid), poly-diethylene glycol adipate, nucleator and oxidation inhibitor is 100:(10～40): (0.3～1): (0.3～1).
2. a kind of complete biodegradable plasticized poly lactic acid resin according to claim 1, is characterized in that, the number-average molecular weight of described poly(lactic acid) is 50000～200000 dalton.
3. a kind of complete biodegradable plasticized poly lactic acid resin according to claim 1, is characterized in that, the number-average molecular weight of described poly-diethylene glycol adipate is 1000～20000 dalton.
4. a kind of complete biodegradable plasticized poly lactic acid resin according to claim 1, is characterized in that, described nucleator is multiamide compounds or calcium carbonate load phenyl-phosphonic acid calcium.
5. a kind of complete biodegradable plasticized poly lactic acid resin according to claim 4, is characterized in that, described multiamide compounds is TMC-300 or TMC-328.
6. a kind of complete biodegradable plasticized poly lactic acid resin according to claim 1, it is characterized in that, described oxidation inhibitor is the mixture of four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.
7. a kind of complete biodegradable plasticized poly lactic acid resin according to claim 6, it is characterized in that, described four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) weight ratio of pentaerythritol ester and tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is 1:(1.5～2.5).
8. the preparation method of a complete biodegradable plasticized poly lactic acid resin, is characterized in that, comprises as follows:
After being mixed, poly(lactic acid), nucleator and oxidation inhibitor adds poly-diethylene glycol adipate, obtain mixture, with said mixture at 130 ℃～195 ℃ blending extrusions, obtain polylactic resin, the blending ratio of described poly(lactic acid), poly-diethylene glycol adipate, nucleator and oxidation inhibitor is by weight: 100:(10～40): (0.3～1): (0.3～1).
9. the preparation method of a kind of complete biodegradable plasticized poly lactic acid resin according to claim 8, is characterized in that, the number-average molecular weight of described poly-diethylene glycol adipate is 1000～20000 dalton.
10. the preparation method of a kind of complete biodegradable plasticized poly lactic acid resin according to claim 8, is characterized in that, described nucleator is multiamide compounds or calcium carbonate load phenyl-phosphonic acid calcium.
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| CN105602214A (en) * | 2016-01-14 | 2016-05-25 | 中国科学院长春应用化学研究所 | Plasticized and toughened modified polylactic acid and preparation method thereof |
| CN105597139A (en) * | 2015-12-17 | 2016-05-25 | 张德信 | Medical suture line used for surgeries and preparation method |
| CN111363323A (en) * | 2020-03-02 | 2020-07-03 | 浙江农林大学 | Preparation method and application of slow-release antioxidant membrane |
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| CN111363323A (en) * | 2020-03-02 | 2020-07-03 | 浙江农林大学 | Preparation method and application of slow-release antioxidant membrane |
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Application publication date: 20130619 |